Isoindolineazo pigments

ABSTRACT

Isoindolineazo pigments of the general formula I ##STR1## where A is the radical of an active-methylene compound or ═S; 
     L is substituted or unsubstituted 1,4-phenylene, 1,3-phenylene or 1,5-naphthylene; 
     K is the radical of a coupling component K--H; and the benzene ring D is optionally substituted, 
     are useful for pigmenting high polymer organic materials.

The present invention relates to novel isoindolineazo pigments of the general formula I ##STR2## where: A is a radical of the formula ##STR3## where: R¹ is

cyano;

carbamoyl, with or without substitution by ##STR4## or 3,3,5,5-tetramethyl-4-piperidyl, by C₁ -C₁₈ -alkyl, C₁ -C₁₀ -alkoxycarbonyl, benzyl, phenyl or naphthyl, which substituents may in turn be substituted by halogen, cyano, nitro, sulfo, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkylcarbonyl, C₁ -C₁₀ -alkoxycarbonyl, mono (C₁ -C₁₀ -alkyl)amino, di(C₁ -C₁₀ -alkyl) amino, formylamino, C₂ -C₁₀ -alkanoylamino, benzoylamino, aminosulfonyl, mono- or di(C₁ -C₁₀ -alkyl)aminosulfonyl, phenylazo, 3,3,5,5-tetramethyl-4-piperidyl, phthalimidyl, carbamoyl, which can be C₁ -C₁₀ -alkyl- monosubstituted or -disubstituted, and/or by trifluoromethyl;

C₁ -C₁₀ -alkylcarbonyl, benzoyl, C₁ -C₁₀ -alkoxycarbonyl, phenoxycarbonyl or benzyloxycarbonyl, wherein benzoyl, phenoxy and benzyloxy may be substituted by halogen, nitro, sulfo, C₁ -C₁₀ -alkyl, formylamino, C₂ -C₁₀ -alkanoylamino and/or phthalimidyl;

phenyl, which may be substituted by halogen, cyano, nitro, sulfo and/or trifluoromethyl;

carbazoyl or ureidocarbonyl, whose terminal nitrogen atoms may be substituted once or twice by C₁ -C₁₀ -alkyl or benzyl which can carry the abovementioned substituents; a heterocyclic radical of the formula ##STR5## where Z is --O--, --S-- or --NH--,

R⁶ is halogen, nitro, sulfo, C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy,

R⁷ is halogen,

p is from 0 to 2, and

q is from 1 to 4;

R² is independently in each appearance hydrogen, C₁ -C₁₀ -alkyl, phenyl or naphthyl, which may each be substituted by halogen, nitro, sulfo, C₁ -C₁₀ -alkyl and/or C₁ -C₁₀ -alkoxy;

R³ is C₁ -C₁₀ -alkyl, amino, benzoylamino, carboxyl, carbamoyl or C₁ -C₁₀ -alkoxycarbonyl;

R⁴ is hydrogen or phenyl which may carry up to two of the following substituents: halogen, nitro, sulfo, carboxyl, carbamoyl, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy or C₁ -C₁₀ -alkoxycarbonyl;

R⁵ is halogen or nitro;

X is --O-- or --NR⁸ -- where R⁸ is hydrogen or C₁ -C₁₀ -alkyl;

m is from 0 to 4;

L is 1,4-phenylene, 1,3-phenylene or 1,5-naphthylene, which may each carry the following substituents: halogen, nitro, carboxyl, sulfo, sulfonamido, which may be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkylcarbonyl, C₁ -C₁₀ -alkoxycarbonyl, formylamino, C₂ -C₁₀ -alkanoylamino and/or carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or disubstituted;

K is the radical of a coupling component of the formula ##STR6## where R⁸ is hydrogen, halogen, nitro, sulfo, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkoxycarbonyl and/or carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted;

R⁹ is C₁ -C₁₀ -alkyl, which may be substituted by amino or mono- or di(C₁ -C₁₀ -alkyl)amino;

R¹⁰ is hydrogen, halogen, cyano, sulfo, C₁ -C₁₀ -alkylcarbonyl, C₁ -C₁₀ -alkoxycarbonyl or carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted;

R¹¹ is methyl or phenyl which may carry the following substituents: halogen, hydroxyl, nitro, sulfo, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkylcarbonyl, C₁ -C₁₀ -alkoxycarbonyl, formylamino, C₂ -C₁₀ -alkanoylamino, carboxyl, carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or disubstituted, mono- or di(C₁ -C₁₀ alkyl) or -(phenyl)aminosulfonyl and/or C₁ -C₁₀ -alkoxy- or phenoxy-sulfonyl;

R¹² is hydrogen, halogen, hydroxyl, sulfo, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxyl C₁ -C₁₀ -alkylcarbonyl, carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted, and/or mono(C₁ -C₁₀ -alkyl)- or -(phenyl)aminosulfonyl;

R¹³ is identical or different radicals; hydrogen, C₁ -C₁₀ -alkyl or C₁ -C₁₀ alkylcarbonyl;

R¹⁴ is hydroxyl or a radical of the formula

    --NH--R.sup.20

where R²⁰ is hydrogen, phenyl which may carry the substituents mentioned for phenyl under R¹⁰, or a heterocyclic radical of the formula ##STR7## R¹⁵ is phenyl or naphthyl which may each carry the substituents mentioned for phenyl under R²⁰, or one of the heterocyclic radicals R²⁰ mentioned under R¹⁴ ;

R¹⁶ is methyl or a radical of the formula --NH--R¹⁵ ;

R¹⁷ is hydrogen or sulfo;

R¹⁸ is hydrogen or hydroxyl;

R¹⁹ is halogen;

Y is --O-- or --CH₂ --;

Z is ═O or ═S;

the benzene ring D may be substituted by halogen, nitro, carboxyl, carbamoyl, C₁ -C₁₀ -alkyl and/or C₁ -C₁₀ alkoxy;

and the pigments may be present in the azo or the hydrazo form or in the form of an equilibrium mixture between these two forms and the lakable groups present may be laked.

The novel isoindolineazo pigments, depending on the coupling component, can be present in the azo or in the hydrazo form or in the form of an equilibrium mixture.

The present invention further relates to the preparation of these pigments and to their use for pigmenting macromolecular organic materials.

Isoindolines are an interesting class of pigments for the yellow to red and also brown to black range of hues.

Azo pigments based on isoindolines have so far not been described. Only azo pigments based on isoindolinones (DE-A-29 01 121 and EP-A-22 076) are known.

It is an object of the present invention to provide novel azo pigments which are based on isoindoline and have advantageous application properties and so allow a wider scope for variation as regards the desired hue and the desired application properties.

We have found that this object is achieved by the isoindolineazo pigments of the above-defined formula I.

We have further found a process for preparing isoindolineazo pigments I, which comprises reacting a half-condensate of the formula II ##STR8## with an aromatic diamine of the formula III

    --H.sub.2 N--L--NH.sub.2                                   III

in an organic solvent which is inert under the reaction conditions and diazotizing the resulting amine of the formula IV ##STR9## and coupling it with a coupling component K--H (V).

Lastly, we have found that the isoindolineazo pigments I are useful for pigmenting high polymer organic materials.

The benzene ring D may carry up to 4 of the following substituents: halogen, nitro, carboxyl, carbamoyl, C₁ -C₆ -alkyl and/or C₁ -C₆ -alkoxy. Preferably, however, it is unsubstituted.

Suitable radicals A besides sulfur conform in particular to the following radicals of active-methylene compounds with formulae (AI) to (AXI): ##STR10## where R¹ has the following meanings: cyano;

carbamoyl, with or without substitution by ##STR11## or 3,3,5,5-tetramethyl-4-piperidyl, by C₁ -C₁₈ -alkyl, C₁ -C₁₀ -alkoxycarbonyl, benzyl, phenyl or naphthyl, which substituents may in 30 turn be substituted by halogen, cyano, nitro, sulfo, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkylcarbonyl, formylamino, C₂ -C₁₀ -alkanoylamino, C₁ -C₁₀ -alkoxycarbonyl, in particular acetyl, mono- or di(C₁ -C₁₀ -alkylamino), benzoylamino, aminosulfonyl, mono- or di(C₁ -C₁₀ -alkyl)aminosulfonyl, phenylazo, 3,3,5,5-tetramethyl-4-piperidyl, phthalimidyl, carbamoyl, which can be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted, and/or by trifluoromethyl;

C₁ -C₁₀ -alkylcarbonyl, benzoyl, C₁ -C₁₀ -alkoxycarbonyl, phenoxycarbonyl or benzyloxycarbonyl, wherein benzoyl, phenoxy and benzyloxy may be substituted by halogen, nitro, sulfo, C₁ -C₁₀ -alkyl, formylamino, C₂ -C₁₀ -alkanoylamino and/or phthalimidyl; phenyl, which may be substituted by halogen, cyano, nitro, sulfo and/or trifluoromethyl;

carbazoyl or ureidocarbonyl, whose terminal nitrogen atoms may be substituted once or twice by C₁ -C₁₀ -alkyl or benzyl which can

carry the abovementioned substituents; a heterocyclic radical of the formula ##STR12## where Z is --O--, --S--or --NH--,

R⁶ is halogen, nitro, sulfo, C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy,

R⁷ is halogen,

p is from 0 to 2, and

q is from 1 to 4; ##STR13## where R² is independently in each appearance hydrogen, C₁ -C₁₀ -alkyl, phenyl or naphthyl, which may each be substituted by halogen, nitro, sulfo, C₁ -C₁₀ -alkyl and/or C₁ -C₁₀ -alkoxy; ##STR14## where R³ is C₁ -C₁₀ -alkyl, in particular methyl, amino, benzoylamino, carboxyl, carbamoyl or C₁ C₁₀ alkoxycarbonyl;

R⁴ is hydrogen or phenyl which may carry up to two of the following substituents: halogen, in particular chlorine, nitro, sulfo, carboxyl, carb-amoyl, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy or C₁ -C₁₀ -alkoxycarbonyl; ##STR15## where X is --O-- or --NR⁸ --, where R⁸ is hydrogen or C₁ -C₁₀ -alkyl, in particular methyl,

R⁵ is halogen, in particular chlorine or nitro;

m is from 0 to 4; ##STR16##

The radicals A of the formula (AI) are mentioned as preferred.

Suitable bridge members L are besides 1,5-naphthylene particularly 1,3-phenylene and very particularly 1,4-phenylene.

The benzene and naphthalene rings may each carry up to two identical or different ones of the following substituents: halogen, nitro, carboxyl, sulfo, sulfonamido, which may be C₁ -C₁₀ -alkylcarbonyl-monosubstituted or -disubstituted, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkylcarbonyl, C₁ -C₁₀ -alkoxycarbonyl, formylamino, C₂ -C₁₀ -alkanoylamino and/or carbamoyl which may be C₁ -C₁₀ -alkyl- monosubstituted or disubstituted.

Preference here is given to the substituents chlorine, bromine, methyl, methoxy, sulfo, sulfonamido and carbamoyl.

Preferably, however, the aromatic rings are unsubstituted.

Suitable radicals K of the coupling components K--H (V) conform to the formulae (KI) to (KXVIII): ##STR17## where R¹ is as defined above; ##STR18## where Y is --O-- or --CH₂ --; ##STR19## where Z is ═O or ═S and R² is as defined above; ##STR20## where R³ and R⁴ are each as defined above; ##STR21## where R³ is as defined above, q is from 1 to 4 and

R⁸ is hydrogen, halogen, nitro, sulfo, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkoxycarbonyl and/or carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted; ##STR22## where R⁹ is C₁ -C₁₀ -alkyl, which may be substituted by amino or mono- or di(C₁ -C₁₀ -alkyl)amino;

R¹⁰ is hydrogen, halogen, cyano, sulfo, C₁ -C₁₀ -alkylcarbonyl, C₁ -C₁₀ -alkoxycarbonyl or carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted; ##STR23## where R¹¹ is methyl or phenyl which may carry the following substituents: halogen, hydroxyl, nitro, sulfo, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkylcarbonyl, formylamino, C₂ -C₁₀ -alkanoylamino, carbamoyl which may be (C₁ -C₁₀ -alkyl)-monosubstituted or disubstituted, mono- or di(C₁ -C₁₀ alkyl) or -(phenyl)aminosulfonyl and/or C₁ -C₁₀ -alkoxy- or phenoxy-sulfonyl;

R¹² is hydrogen, halogen, hydroxyl, sulfo, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkylcarbonyl, carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted, and/or mono(C₁ -C₁₀ -alkyl)- or -(phenyl)aminosulfonyl; ##STR24## where R⁸ is as defined above and

R¹³ is identical or different radicals, hydrogen, C₁ -C₁₀ -alkyl or C₁ -C₁₀ -alkylcarbonyl; ##STR25## where R¹⁴ is hydroxyl or a radical of the formula

    --NH--R.sup.20

where R²⁰ is hydrogen, phenyl which may carry the substituents mentioned for phenyl under R¹⁰, or a heterocyclic radical of the formula ##STR26## where R¹⁵ is phenyl or naphthyl which may each carry the substituents mentioned for phenyl under R¹⁰, or one of the heterocyclic radicals R²⁰ mentioned under R¹⁴ ;

R¹⁶ is methyl or a radical of the formula --NH--R¹⁵ ; ##STR27## where R¹⁷ is hydrogen or sulfo;

R¹⁸ is hydrogen or hydroxyl;

R¹⁹ is halogen.

The radicals of preferred coupling components are the radicals of the formulae (KIV) and (KVI).

Examples of the aforementioned radicals are:

C₁ -C₁₈ -alkyl, preferably C₁ -C₁₀ -alkyl, particularly preferably C₁ -C₆ -alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl and 2-methylpentyl, in particular methyl and ethyl;

C₁ -C₁₀ -alkoxy, preferably C₁ -C₆ -alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy and hexyloxy, in particular methoxy and ethoxy;

C₁ -C₁₀ -alkylcarbonyl, preferably C₁ -C₆ -alkylcarbonyl, such as acetyl, propionyl, in particular acetyl;

C₁ -C₁₀ -alkoxycarbonyl, preferably C₁ -C₆ -alkoxycarbonyl, such as in particular methoxycarbonyl and ethoxycarbonyl;

mono- and di(C₁ -C₁₀ -alkyl)amino, preferably mono- and di(C₁ -C₆ -alkyl)amino, such as methylamino, ethylamino, propylamino, isopropylamino, butylamino, pentylamino and hexylamino, in particular methylamino and ethylamino; cycloalkylamino such as cyclopropyl-, cyclobutyl-, cyclopentyl- and cyclohexyl-amino; dimethylamino, diethylamino, dipropylamino, diisopropylamino and methylethylamino;

C₂ -C₁₀ -alkanoylamino, preferably C₂ -C₇ -alkanoylamino: in particular acetylamino;

mono- and di(C₁ -C₁₀ -alkyl)aminosulfonyl, preferably mono- and di(C₁ -C₆ -alkyl)aminosulfonyl: methyl- and ethyl-aminosulfonyl;

C₁ -C₁₀ -alkoxysulfonyl, preferably C₁ -C₆ -alkoxysulfonyl: methoxy- and ethoxy-sulfonyl;

halogen: in particular chlorine and bromine.

If the isoindolineazo pigments I contain lakable groups such as carboxyl or sulfo, these can also be present in laked form, ie. as metal salts.

Suitable metals here include for example lithium, sodium, potassium, strontium, barium, aluminum, copper, iron, cobalt, nickel and in particular magnesium, calcium, zinc and manganese.

In the novel process for preparing the isoindolineazo pigments I, first a half-condensate II is reacted with an aromatic diamine III in an organic solvent which is inert under the reaction conditions to give an amine of the formula IV ##STR28## which is then diazotized in a conventional manner and coupled with a coupling component K--H (V), it being surprising that the amine IV is so stable in the acid medium that it can be diazotized.

Suitable inert organic solvents for preparing the amine IV are, as described in German Patent Application P 43 41 769.8, polar protic solvents such as mono- or polyhydric aromatic alcohols and aliphatic alcohols, ether-alcohols, open-chain and cyclic ethers, dipolar aprotic solvents and aromatic solvents such as nitrobenzene, toluene and chlorobenzene.

Specific examples are phenol, C₁ -C₆ -alcohols, preferably C₁ -C₄ -alkanols such as ethanol, propanol, isopropanol, butanol and in particular methanol; ethylene glycol mono- and di(C₁ -C₆ -alkyl) ethers such as ethylene glycol monomethyl and dimethyl ether, oligo- and polyglycols and glycol ethers such as diethylene glycol monomethyl ether, dioxane and tetrahydrofuran; dimethyl sulfoxide and amidic solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone. Also suitable are mixtures of these solvents, for example dimethylacetamide/alkanol, phenol/alkanol.

The amount of solvent is not critical per se and generally ranges from 5 to 100 g, preferably from 10 to 50 g, per g of II.

Half-condensate II and diamine III are advantageously used in substantially equimolar ratio.

The half-condensates II are known per se or are preparable in a known manner by reacting the corresponding iminoaminoisoindolenines, trichloroisoindolenines and appropriately activated derivatives or directly from the corresponding o-phthalodinitriles with active-methylene (acidic C--H) compounds.

Generally, the reaction of II with III is carried out at from 0° to 100° C., in particular at from 30° to 80° C. The temperature to be used also depends on the refluxing temperature of the solvent used.

Typically the reaction is carried out at atmospheric pressure. However, the reaction can also be carried out under superatmospheric pressure.

Typical reaction times range from about 10 min to 5 h, and the reaction will usually have ended after the heating-up phase.

The process is generally carried out by initially charging a heated or unheated mixture of solvent and half-condensate II and adding the aromatic diamine III. This addition may be continuous.

The amine IV is then advantageously isolated and as is generally customary, diazotized and coupled with the coupling component V.

Suitable solvents for the diazotization include in particular dipolar aprotic solvents such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide and water and also mixtures thereof.

The diazotization is carried out in the presence of an organic acid such as acetic acid (glacial acetic acid) and propionic acid or an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.

Suitable diazotizing agents are the compounds customarily used for this purpose such as alkali metal nitrites, in particular sodium nitrite, organic nitrites, in particular glycol nitrite and isoamyl nitrite, and nitrosylsulfuric acid.

The concentration of the reaction mixture is determined by its stirrability.

The reaction temperature depends on the reactivity and stability of the reactants and their solubility and generally ranges from -20° to 50° C., preferably from 0° to 5° C.

After the diazotization has ended, which can take from a few minutes to some hours, the pH required for the coupling (generally a pH from 4 to 6) is set by adding a base such as sodium hydroxide solution and the coupling component, advantageously dissolved in one of the abovementioned solvents, an alcohol or a mixture thereof, if necessary with a base (for example sodium hydroxide solution), is added.

The reaction mixture can be worked up for the isoindolineazo pigments I in a conventional manner by, after the mixture has cooled down, filtering off the pigments, washing them if necessary with an inert solvent such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone or glacial acetic acid, alcohols and/or water, and drying.

Depending on the use requirements, the pigments can be used directly in the form in which they were obtained, or first a customary grinding and/or customary solvent treatment is carried out in the presence or absence of crystallization control additives. Of course, the crystallization can also be controlled even in the course of the synthesis by means of conventional measures such as the addition of crystallization-inhibiting additives, the action of shearing forces during the reaction and the addition of grinding media and/or specific temperature control.

The process of the present invention makes it possible to prepare the isoindolineazo pigments in a specific manner in good yield and purity.

The isoindolineazo pigments I thus obtainable can be used with advantage for coloring macromolecular organic materials. More particular uses are the preparation of printing inks and coatings and the pigmenting of plastics.

Examples of materials to be colored are natural resins; synthetic resins (addition polymerization and condensation resins) such as alkyd resins, acrylic resins, epoxy resins, amino-formaldehyde resins such as melamine and urea resins; cellulose ethers and esters such as ethylcellulose, nitrocellulose, cellulose acetate and butyrate; polyurethanes; polyvinyl chlorides; rubber, chlororubber; polyolefins; polyamides; polyesters; epoxy esters; polycarbonates; phenolic resins; natural rubber; casein; silicone and silicone resins; and also mixtures thereof.

The macromolecular organic materials can be colored as plastic materials, melts, solutions, emulsions or dispersions. Coatings and printing inks are preferably prepared using solutions or dispersions. Examples of preferred coating systems are alkyd/melamine resin coatings, acrylic/melamine resin coatings, cellulose acetate/cellulose butyrate coatings and two-pack coatings based on acrylic resins crosslinkable with polyisocyanate.

EXAMPLES

Preparation of isoindolineazo pigments of the formula ##STR29##

Examples 1 ##STR30## a) Preparation of diazo component IV

To a suspension of 22.6 g of the half-condensate ##STR31## in 300 ml of methanol were added dropwise at room temperature 10.8 g of p-phenylenediamine, dissolved in 100 ml of methanol. The reaction mixture was then stirred for 1 h under reflux.

The solvent was then half distilled off and the precipitate was isolated by filtration, washed with methanol and water and dried.

28.7 g were obtained of the compound ##STR32## as a red powder having a melting point of 285° C., which corresponds to a yield of 90.5%.

Physical data:

Elemental analysis: C: obs. 68.0 (calc. 68.1); H: obs. 4.9 (calc. 4.8); O: obs. 5.5 (calc. 5.0); N: obs. 21.9 (calc. 22.1); MS: m/e=317.0 (C₁₈ H₁₅ ON₅ ⁺);

¹ H-NMR(DMSO-d₆ ; TMS): 2.72-2.73 (d, 1H, NH--CH₃); 2.80-2.82 (d, 2H, NH--CH₃); 3.73 (s, water); 5.29 (s; broad); 5.41 (s; broad); 6.67-6.72 (m, 2H, arom.); 6.94-6.97 (d, 0.6H, arom.); 7.49-7.52 (d, 1.4H, arom.); 7.68-7.71 (m, 2H, arom.); 8.0-8.1 (m, 0.6H, arom.), 8.25-8.37 (m, 1.4H, arom.); 9.91-9.94 (q, 1H, NH--CH₃); 11.27 (broad); 12.01 (mobile protons) ppm;

TLC (Merck silica gel 60 F₂₅₄, ready-made aluminum foil sheets): R_(f) (acetone): 0.8; R_(f) (3:1:1 v/v/v n-butanol/glacial acetic acid/water): 0.82; R_(f) (7:1:1 v/v/v toluene/glacial acetic acid/ethyl acetate): 0.45.

b) Diazotization and coupling

A solution of 15.9 g (0.05 mol) of the diazo component obtained in a), in 100 ml of N-methylpyrrolidone, was admixed at room temperature with 15 ml of concentrated hydrochloric acid. After cooling down to 0° C. 15 ml of 23% strength by weight sodium nitrite solution were added dropwise.

After stirring for one hour at 0°-5° C., first 0.5 g of amidosulfuric acid was added, followed by 9.5 g (0.055 mol) of N-phenylmethylpyrazolone, dissolved in 100 ml of methanol and 3 ml of 30% strength by weight sodium hydroxide solution. The pH was maintained at from 4 to 5.

As soon as the diazo component was no longer detectable (after 2 h) the reaction mixture was warmed to room temperature and filtered.

The isolated precipitate was washed with N-methylpyrrolidone and water and dried at 80° C.

24.1 g were obtained of the target product as a red powder, which corresponds to a yield of 96%.

Elemental analysis: C: obs. 66.5 (calc. 66.92); H: obs. 4.5 (calc. 4.41); O: obs. 6.3 (calc. 6.37); N: obs. 22.1 (calc. 22.3).

To assess the colorimetric properties, 1 g of pigment and 9.5 g of a baking finish mixture of 70% by weight of coco-alkyd resin (60% strength by weight in xylene) and 30% by weight of melamine resin (55% strength by weight in butanol/xylene) were ground in an attritor, applied to a metal sheet, flashed off and baked at 120° C. for 30 min.

A red coating was obtained.

Examples 2 to 52

The method of Example 1 was utilized to prepare the isoindolineazo pigments listed below in the table (coupling pH from 3 to 5) and incorporate them into the abovementioned coating system.

                                      TABLE                                        __________________________________________________________________________      ##STR33##                                                                     Ex.                                                                               K                         Coating color                                     __________________________________________________________________________      2                                                                                 ##STR34##                reddish orange                                     3                                                                                 ##STR35##                reddish orange                                     4                                                                                 ##STR36##                red                                                5                                                                                 ##STR37##                reddish orange                                     6                                                                                 ##STR38##                orange                                             7                                                                                 ##STR39##                reddish brown                                      8                                                                                 ##STR40##                reddish brown                                      9                                                                                 ##STR41##                reddish brown                                     10                                                                                 ##STR42##                dark red                                          11                                                                                 ##STR43##                dark red                                          12                                                                                 ##STR44##                red                                               13                                                                                 ##STR45##                red                                               14                                                                                 ##STR46##                red                                               15                                                                                 ##STR47##                red                                               16                                                                                 ##STR48##                dark red                                          17                                                                                 ##STR49##                red                                               18                                                                                 ##STR50##                dark red                                          19                                                                                 ##STR51##                red                                               20                                                                                 ##STR52##                brown                                             21                                                                                 ##STR53##                brown                                             22                                                                                 ##STR54##                brown                                             23                                                                                 ##STR55##                yellow                                            24                                                                                 ##STR56##                orange                                            25                                                                                 ##STR57##                dark green                                        26                                                                                 ##STR58##                reddish dark brown                                27                                                                                 ##STR59##                violetish black                                   28                                                                                 ##STR60##                brown                                             29                                                                                 ##STR61##                brown                                             30                                                                                 ##STR62##                brown                                             31                                                                                 ##STR63##                blackish red                                      32                                                                                 ##STR64##                brown                                             33                                                                                 ##STR65##                brown                                             34                                                                                 ##STR66##                blackish red                                      35                                                                                 ##STR67##                blackish red                                      36                                                                                 ##STR68##                blackish red                                      37                                                                                 ##STR69##                brown                                             38                                                                                 ##STR70##                blackish brown                                    39                                                                                 ##STR71##                brown                                             40                                                                                 ##STR72##                dark brown                                        41                                                                                 ##STR73##                dark brown                                        42                                                                                 ##STR74##                dark brown                                        43                                                                                 ##STR75##                dark brown                                        44                                                                                 ##STR76##                dark brown                                        45                                                                                 ##STR77##                dark brown                                        46                                                                                 ##STR78##                dark brown                                        47                                                                                 ##STR79##                dark brown                                        48                                                                                 ##STR80##                dark brown                                        49                                                                                 ##STR81##                dark brown                                        50                                                                                 ##STR82##                dark brown                                        51                                                                                 ##STR83##                dark brown                                        52                                                                                 ##STR84##                dark brown                                        __________________________________________________________________________ 

We claim:
 1. Isoindolineazo pigment of the general formula I ##STR85## where: A is a radical of the formula ##STR86## where R¹ iscyano; carbamoyl with or without substitution by ##STR87## or 3,3,5,5-tetramethyl-4-piperidyl, by C₁ -C₁₈ -alkyl C₁ -C₁₀ -alkoxycarbonyl, benzyl, phenyl or naphthyl, which substituents may in turn be substituted by halogen, cyano, nitro, sulfo, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkylcarbonyl, C₁ -C₁₀ -alkoxycarbonyl, mono(C₁ -C₁₀ -alkyl)amino, di(C₁ -C₁₀ -alkyl)amino, formylamino, C₂ -C₁₀ -alkanoylamino, benzoylamino, aminosulfonyl, mono- or di(C₁ -C₁₀ -alkyl)aminosulfonyl, phenylazo, 3,3,5,5-tetramethyl-4-piperidyl, phthalimidyl, carbamoyl, which can be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted, and/or by trifluoromethyl; C₁ -C₁₀ -alkylcarbonyl, benzoyl, C₁ -C₁₀ -alkoxycarbonyl, phenoxycarbonyl or benzyloxycarbonyl, wherein benzoyl, phenoxy and benzyloxy may be substituted by halogen, nitro, sulfo, C₁ -C₁₀ -alkyl, formylamino, C₂ -C₁₀ -alkanoylamino and/or phthalimidyl; phenyl, which may be substituted by halogen, cyano, nitro, sulfo and/or trifluoromethyl; carbazoyl or ureidocarbonyl, whose terminal nitrogen atoms may be substituted once or twice by C₁ -C₁₀ -alkyl or benzyl which can carry the abovementioned substituents; a heterocyclic radical of the formula ##STR88## where Z is --O--, --S-- or --NH--, R⁶ is halogen, nitro, sulfo, C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy, R⁷ is halogen, p is from 0 to 2, and q is from 1 to 4; R² is independently in each appearance hydrogen, C₁ -C₁₀ -alkyl, phenyl or naphthyl, which may each be substituted by halogen, nitro, sulfo, C₁ -C₁₀ -alkyl and/or C₁ -C₁₀ -alkoxy; R³ is C₁ -C₁₀ -alkyl, amino, benzoylamino, carboxyl, carbamoyl or C₁ -C₁₀ -alkoxycarbonyl; R⁴ is hydrogen or phenyl which may carry up to two of the following substituents: halogen, nitro, sulfo, carboxyl, carbamoyl, C₁ -C₁₀ -alkyl, C₁ -C₁₀ alkoxy or C₁ -C₁₀ -alkoxycarbonyl; R⁵ is halogen or nitro; X is --O-- or --NR⁸ --where R⁸ is hydrogen or C₁ -C₁₀ -alkyl; m is from 0 to 4; L is 1,4-phenylene, 1,3-phenylene or 1,5-naphthylene, which may each carry the following substituents: halogen, nitro, carboxyl, sulfo, sulfonamido, which may be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkylcarbonyl, C₁ -C₁₀ -alkoxycarbonyl, formylamino, C₂ -C₁₀ -alkanoylamino and/or carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or disubstituted; K is the radical of a coupling component of the formula ##STR89## where R⁸ is hydrogen, halogen, nitro, sulfo, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkoxycarbonyl and/or carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted;R⁹ is C₁ -C₁₀ -alkyl, which may be substituted by amino or mono- or di(C₁ -C₁₀ -alkyl)amino; R¹⁰ is hydrogen, halogen, cyano, sulfo, C₁ -C₁₀ -alkylcarbonyl, C₁ -C₁₀ -alkoxycarbonyl or carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted; R¹¹ is methyl or phenyl which may carry the following substituents: halogen, hydroxyl, nitro, sulfo, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkylcarbonyl, C₁ -C₁₀ -alkoxycarbonyl, formylamino, C₂ -C₁₀ -alkyanoyamino, carboxyl, carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or disubstituted, mono-or di(C₁ -C₁₀ alkyl) or -(phenyl)aminosulfonyl and/or C₁ -C₁₀ -alkoxy- or phenoxy-sulfonyl; R¹² is hydrogen, halogen, hydroxyl, sulfo, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -alkylcarbonyl, carbamoyl which may be C₁ -C₁₀ -alkyl-monosubstituted or -disubstituted, and/or mono(C₁ -C₁₀ -alkyl)- or -(phenyl)aminosulfonyl; R¹³ is identical or different radicals: hydrogen, C₁ -C₁₀ -alkyl or C₁ -C₁₀ -alkylcarbonyl; R¹⁴ is hydroxyl or a radical of the formula

    --NH--R.sup.20

where R²⁰ is hydrogen, phenyl which may carry the substituents mentioned for phenyl under R¹⁰, or a heterocyclic radical of the formula ##STR90## R¹⁵ is phenyl or naphthyl which may each carry the substituents mentioned for phenyl under R¹⁰, or one of the heterocyclic radicals R²⁰ mentioned under R¹⁴ ; R¹⁶ is methyl or a radical of the formula --NH--R¹⁵ ; R¹⁷ is hydrogen or sulfo; R¹⁸ is hydrogen or hydroxyl; R¹⁹ is halogen; Y is --O-- or --CH₂ --; Z is ═O or ═S; the benzene ring D may be substituted by halogen, nitro, carboxyl, carbamoyl, C₁ -C₁₀ -alkyl and/or C₁ -C₁₀ -alkoxy;and the pigments may be present in the azo or the hydrazo form or in the form of an equilibrium mixture between these two forms and the lakable groups present may be laked.
 2. Isoindolineazo pigment of the formula I as claimed in claim 1 whereinA is a radical of the formula ##STR91## L is 1,4-phenylene and K is a radical of the formula ##STR92##
 3. A process for pigmenting high polymer organic materials, which comprises incorporating into said material an isoindolineazo pigment of the formula I as set forth in claim
 1. 